Fungicidal and nematocidal compositions and methods of combating fungi or nematodes using n-(4-homo-3 - halophenyl)-n&#39; - lower alkyl - n&#39;-lower alkoxy-urea

ABSTRACT

THIS INVENTION RELATES TO THE USE AS FUNGICIDES AND NEMATOCIDES OF COMPOUNDS HAVING THE FORMULA   1-BR,2-(HAL),4-(R1-O-N(-R2)-CO-NH-)BENZENE   WHEREIN HAL REPRESENTS BROMINE OR CHLORINE AND R1 AND R2 EACH REPRESENTS A LOWER ALKYL.

United States Patent Olfice 3,702,363 Patented Nov. 7, 1972 3,702,363 FUNGICIDAL AND NEMATOCIDAL COMPOSI- TIONS AND METHODS OF COMBATING FUNGI R NEMATODES USING N-(4-HOMO- 3 HALOPHENYL)-N' LOWER ALKYL N- LOWER ALKOXY-UREA Henry Martin, Basel, Hans Aebi, Riehen, and Ludwig Ebner, Stein, Aargau, Switzerland, assignors to Ciba- Geigy AG, Basel, Switzerland No Drawing. Division of application Ser. No. 870,916, Oct. 2, 1969, now Patent No. 3,617,249, which is a division of application Ser. No. 543,541, Apr. 19, 1966, now Patent No. 3,497,541, which in turn is a continuation-in-part of application Ser. No. 191,442, May 1, 1962, now Patent No. 3,288,851. This application May 21, 1971, Ser. No. 145,949

Int. Cl. A01n 9/12, 9/20 U.S. Cl. 424-322 Claims ABSTRACT OF THE DISCLGSURE This invention relates to the use as fungicides and nematocides of compounds having the formula wherein Hal represents bromine or chlorine and R and R each represents a lower alkyl.

This is a divisional application of our application Ser. No. 870,916, filed Oct. 2, 1969, now US. Pat. No. 3,617,249, which is, in turn, a divisional application of our application Ser. No. 543,541, filed Apr. 19, 1966, now US. Pat. No. 3,497,541. Application Ser. No. 543,541 is a continuation-in-part of our application Ser. No. 191,442, filed May 1, 1962, now US. Pat. No. 3,288,851.

The present invention relates to new compounds of the general formula Hal wherein Hal represents a halogen atom, more particularly a bromine or chlorine atom and R and R each represents a lower alkyl radical.

As a preferred embodiment the present invention relates to the compound of the formula OCH:

II i 0 wherein Hal, R and R have the meaning set forth above in Formula I, with a brominating agent. This process has the advantage that it leads to the production of the valuable compounds of the general Formula I in an especially simple and economical manner. The smooth and unitary course of the reaction could not be foreseen, since the starting materials to be brominated contain other reactive groups, for example, the

group into which the bromine might be expected to enter.

As starting material to be brominated by this process there is especially to be mentioned the compound of the formula OCH:

The bromination of the starting compounds may be carried out in the presence or absence of water.

The urea derivatives used as starting materials are advantageously brominated in the presence of a solvent or dispersing medium in which they are dissolved or suspended and, if desired, in the presence of an agent capable of binding acid, for example, sodium acetate.

As solvents or dispersing media for the starting materials to be brominated there may be used, for example, glacial acetic acid, chloroform, carbon tetrachloride, nitrobenzene, sulfuric acid, water or pyridine.

The bromination may be carried out with bromine itself or with a compound yielding bromine. There may be used organic and inorganic compounds containing bromine that are known to be suitable for brominating organic substances and compounds which yield bromine of their own accord or liberate bromine during the reaction. Examples are: hypobromous acid or salts thereof, especially alkali metal salts or alkaline earth metal salts, such as sodium hypobromite or calcium hypobromite, organic compounds that yield bromine, such as N-bromo-carboxylic acid amides or imides, especially N-bromo-succinimide, addition compounds of bromine with organic compounds, for example with pyridine, such as pyridine dibromide and similar brominating agents. The brominaton is advantageously carried out at temperatures between 60 C. and 100 0., preferably at temperatures between 65 and C.

The invention also provides preparations for combating undesirable plant growth and pests, more particularly harmful nematodes, microorganisms such as fungi, which comprise as 'an active substance a compound of the above general formula, and an inert carrier, a solvent, a diluent,

an emulsifier, a dispersing agent, a wetting agent, an adhesive agent, a fertilizer, or another fungicide, bactericide, a nematocide, or an insecticide, or another herbicide or a molluscicide.

Among the aforesaid preparations those which are specially suitable as pesticides or herbicides are those which contain as active substance the compound of the formula OCH;

if desired, with the use of xylene mixtures, cyclohexanols, ketones, or chlorinated hydrocarbons, such as tetrachlorethane, trichlorethylene or trior tetra-chlorobenzenes.

As preparations that can be diluted with water to yield aqueous liquors for application as such there may be mentioned emulsion concentrates, pastes or wettable powders. As emulsifying or dispersing agents there are used nonionic products, such as condensation products of aliphatic alcohols, amines or carboxylic acids containing a hydrocarbon radical having to 30 carbon atoms with ethylene oxide, such as a condensation product of octadecyl alcohol with to 50 mols of ethylene oxide or of soya bean oil fatty acid with mols of ethylene oxide or of commercial oleylamine with 15 mols of ethylene oxide or of dodecyl mercaptan with 12 mols of ethylene oxide. As anionic emulsifying agents there may be mentioned the sodium salt of dodecyl alcohol sulfuric acid ester, the sodium salt of dodecyl-benzene sulfonic acid, the potassium or triethanolamine salt of oleic acid or of abietic acid or of a mixture of these acids, or the sodium salt of a petroleum sulfonic acid. As cationic dispersing agents there may be used quaternary ammonium compounds, such as cetyl-pyridinium bromide or dihydroxyethyl-benzyl-dodecyl-ammonium chloride.

As solid carriers for making dusting or strewing powders there may be used talcum, kaolin, bentonite, calcium carbonate or calcium phosphate, or carbon cork meal or wood meal or other materials of vegetable origin. It is very advantageous to make up the preparations in a granulated form. The preparations in their various forms may also have incorporated therewith in the usual manner substances that improve their dispersibility, adhesion, resistance to rain or penetrating power, such as fatty acids, resins, glue, casein or, for example, alginates. The preparations that have a selective action may also be used in conjunction with, for example, in admixture with a fertilizer.

EXAMPLE 1 OCH;

107 grams of N-(3-chloro-phenyl)-N'-methoxy-N'- methyl-urea are dissolved in 500 cc. of glacial acetic acid, 41 grams of anhydrous sodium acetate are added, and the bromination is carried out at 80 C. with 80 grams Br dissolved in glacial acetic acid. After 1 hour at 80, the mixture is poured into ice.

The yield of crude N-(4-bromo-3-chlorophenyl)-N- methyl-N-meth0xy-urea is 121 grams. The product melts at 94-96 C. after recrystallization from acetonitrile, melts at 94.5 to 95.5 C.

Analysis.-Calcd. for C H 0 N BrCl (percent): C, 36.82; H, 3.43. Found (percent): C, 36.9; H, 3.3.

EXAMPLE 2 (a) To 10 parts of the compound of the above Example l are added 2 parts of sulfite cellulose waste liquor and 100 cc. of Water, and the mixture is then subjected to intense grinding, to yield a stable dispersion of fine particle size which may be diluted as required with water.

(b) To parts of the compound of Example 1 are added 40 parts of kaolin (Bolus alba), 3.5 parts of a condensation product of 1 mol of para-tertiary octylphenol with 8 mols of ethylene oxide, 1.5 parts of heptadecenylbenzimidazole sulfonate and 5 parts of finely divided SiO the mixture is then subjected to intense grinding, to yield a stable dispersion of fine particle size which may be diluted as required with water.

4 EXAMPLE 3 (a) An aqueous dilution of the dispersion according to Example 2(b) was applied as a spray to a field planted with Irish potatoes (variety: Red Pontiac) at the rates of 1.5 and 3 pounds of active substance per acre, 2 days after the planting of the potatoes.

The following weeds were present in the test field:

Common Name: Scientific name Goosegrass Eleunine indica. Crabgrass Digitaria sanguinalis. Pangolagrass Digitaria decumbena. Bermudagrass Cynodon dactylon. Bahiagrass Paspalum notatum. Pokeweed Phytolacca americana.

At the weed evaluation 2 months after the treatment, all the weeds present in the test field were completely or almost completely killed. There was no phytotoxicity observed on the potatoes treated. At the yield evaluation 3 months after the planting date there was observed that the test field treated according to the invention yielded at least /2. more potatoes than an untreated control field. Good selective herbicidal effects were also obtained according to the method described in this example with an application rate of 0.5 pound of active substance per acre.

EXAMPLE 4 Aqueous dilutions of the dispersion according to Example 2(b) were applied as sprays at rates decreasing from 8 to 0.25 pounds of active substance per acre to cultures of rice plants (paddy rice) in the following manner:

(1) Pre-plant soil incorporation. (Han-owed into the soil two days before the rice was sown.)

(2) Preemergent application. (Spraying of the field 1 day after the sowing of the rice.)

Evaluation In the case of 1: 7 weeks after the treatment In the case of 2: 7 weeks after the treatment Results At the time of the evaluation an untreated control field was heavily infested with junglerice (Panicum) as the only weed present. In the case of the test fields treated according to the methods 1 and 2 set forth above, it was observed that at the rate of 0.5 pound per acre of active substance the rice cultures were completely freed from the junglerice.

EXAMPLE 5 An aqueous dilution of the dispersion according to Example 2(b) was applied as a spray to a field sown with corn at a rate of 0.5 pound of active substance per acre, 2 days after the sowing of the corn.

At the weed evaluation, 4 weeks after the treatment, it was observed that the following weeds which had been predominant in the treated field, were completely killed: lovegrass, crabgrass and pigweed. There was no phytotoxicity observed on the treated corn.

EXAMPLE 6 An aqueous dilution of the dispersion according to Example 2(b) was applied as a spray to a field sown with cotton at a rate of 0.5 pound of active substance per acre, 2 days after the sowing of cotton plants.

At the weed evaluation, 4 weeks after the treatment, it was observed that the following weeds which had been predominant in the treated field, were completely killed: lovegrass, crabgrass and pigweed. There was no phytotoxicity observed on the treated cotton plants.

EXAMPLE 7 Aqueous dilutions of the dispersion according to Example 2(b) were applied as sprays at rates decreasing from 4 to 1 pound of active substance per acre by preplant soil incorporation to tomatoes (harrowed into the soil two days before the tomatoes were planted).

At the evaluation 4 weeks after the treatment of the soil it was observed that the following weeds present in the cultures were killed as a result of the treatment at a rate of 1.0 pound of active substance per acre: deck, whiteclover and pepperweed. No phytotoxicity was observed in the tomatoes.

EXAMPLE 8 An aqueous dilution of the dispersion according to Example 2(b) was applied as a spray to a field sown with peanuts at a rate of 0.5 pound of active substance per acre, 2 days after the sowing of peanuts.

At the weed evaluation, 4 weeks after the treatment, it was observed that the following weeds which had been predominant in the treated field, were completely killed: lovegrass, crabgrass and pigweed. There was no phytotoxicity observed in the treated peanut culture.

EXAMPLE 9 (a) Aqueous dilution of the dispersion according to Example 2(b) were applied as sprays at rates of 0.75 and 1.5 pounds of active substance per acre to culture of carrots, 2 Weeks after the crops had been sown. At the evaluation 4 weeks after the treatment, it was observed that the following weeds which had been predominant in the treated test field, were practically completely killed: lambsquarter, ragweed and smartweed. No phytotoxic effects on the treated carrots were observed.

(b) An equally good selective effect was observed by applying the active compound under the conditions set forth above under (a) to a culture of peas.

EXAMPLE 10 An aqueous dilution of the dispersion according to Example 2(b) was applied as a spray to 2 test fields sown with lima beans and soybeans, respectively at a rate of 0.5 pound of active substance per acre, 2 days after the sowing of said plants.

At the Weed evaluation, 4 weeks after the treatment, it was observed that the following weeds which had been predominant in the treated fields, were completely killed: lovegrass, crabgrass and pigweed. There was no phytotoxicity observed in the treated crop plants.

EXAMPLE 11 Microbicidal effects (a) From the compound described in Example 1 a solution of 1 percent by weight in propylene glycol was prepared and tested against harmful fungi as described below:

(b) The following test-organism was used: Rhizopus nigricans. An aqueous beerwort solution of 10% strength was used as nutrient medium of which 9.5 ml. were put into a test-tube. 0.5 ml. of the solution set forth above under (a) was added to the 9.5 ml. of nutrient medium. In this way a solution was obtained containing 500 p.p.m. of active substance. This was diluted with beerwort solution to a concentration of active substance of 60 p.p.m. The resulting solution was inoculated with 1 drop of a spore suspension of the above mentioned test organisms, and incubated for 8 days at 24 C. It was then determined whether or not any growth of the test organism could be observed. The result is shown in the following table:

Test organism Limit concentration at which inhibition of growth occurs.

Rhizopus nigricans 6O p.p.m.

6 The effective amount of active compound set forth above did not cause any phytotoxic effects on test plants treated with them, e.g. celery plants.

(c) As a comparative test the following compound was tested under exactly the same conditions as set forth above under (a) and (b):

In the case of this compound, however, no fungicidal effect could be observerd, i.e., the test solution was completely overgrown by the test organism.

EXAMPLE l2 OCH;

Nematocidal effect Percent mortality of Panegrellus redivivus Active substance according to application (2.5

p.p.m.)

(b) As a comparative test the following compound was tested under exactly the same conditions as set forth above under (a):

In the case of this compound, however, no nematocidal effect could be observed, i.e., the test organisms, Panegrellus redivivus, were not killed by this compound.

What is claimed is: 1. A method for combating phytopathogenic fungi which comprises applying to said fungi a fungicidally effective amount of a compound of the formula wherein Hal is chlorine and R and R each represents lower alkyl.

2. The method of claim 1 wherein the compound is the one of the formula OCH:

O OCH;

OCH;

3. A method for combating nematodes which comprises applying to said nematodes a nematocidally effective amount of a compound of the formula 8 wherein Hal is chlorine and R and R each represents 0 lower alkyl. g 4. The method of claim 3 wherein the compound is the Br NH one of the formula Hal OCH; wherein Hal is chlorine and R and R each represent 0 Br lower alkyl and a carrier.

1 10 References Cited UNITED STATES PATENTS 3,288,586 11/1966 Little 71120X 5. A fungicidal or nematocidal composition comprising a fungicidally or nematocidally effective amount of 15 JEROME GOLDBERG Pnmary Examiner a compound of the formula A. J. ROBINSON, Assistant Examiner UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,702,363 Dated November 7, 1972 Inventor-(s) Henry Martin et a1.

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In Claim 2, the structural formula should appear as O OCH NH} 4 c N (SEAL) Attest:

' MCCOY M. GIBSON JR.

Attesting Officer c. MARSHALL DANN Conmissionerpf Patents FORM (10-59) USCOMM-DC scan-P59 V [1.5. GOVERNMENT PRINTING OFFICE Z 9 59 '-366-33l' 

